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    • 专利摘要:
    Adsorption purification plant for a gaseous flow comprising at least one corrosive impurity with respect to carbon steel, comprising a radial adsorber comprising: a ferrule with an outer casing of carbon steel; - a vertical perforated internal grid of corrosion resistant material; - an external grid vertical and perforated; an adsorbent maintained vertically by the external grid and the internal grid making it possible to at least partially stop said corrosive impurity; and means for centrifugal circulation of the gas stream.
    公开号:FR3019060A1
    申请号:FR1452705
    申请日:2014-03-28
    公开日:2015-10-02
    发明作者:Elise Renou；Christian Monereau；Thierry Gesbert；Romain Bonay
    申请人:Air Liquide SA；LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a purification plant by adsorption of a gas stream comprising at least one corrosive impurity vis-à-vis the carbon steel. Adsorption is widely used to purify or separate gases. The separation of n and iso paraffins, the separation of xylenes, alcohols, the production of nitrogen or oxygen from atmospheric air, the deballasting of flue gases, blast furnace gas, etc. etc. On the purification side, we find the dryers, the purification of hydrogen or helium, the purification of methane-rich gases, the adsorption of trace impurities in many fluids (mercury stoppage, NOx, sulfur products, etc.). ). Processes employing adsorption are of several types depending on whether the adsorbent is regenerable or not in situ. We therefore speak of adsorption "lost load" that is to say to renew when the product is saturated with impurities (we also use in this case the term "guard bed" to qualify such purification) or adsorption cycles in the other case. The adsorption cycles differ primarily in the way the adsorbent is regenerated. If the regeneration is essentially by increasing the temperature, it is a TSA (Temperature Swing Adsorption = adsorption with temperature variation). If, on the other hand, the regeneration is carried out by lowering the pressure, it is a PSA process (Pressure Swing Adsorption = adsorption at modulated pressure). By PSA process is meant: the PSA processes proper, that is to say with the adsorption phase which is carried out at a pressure substantially higher than the atmospheric pressure, and the regeneration phase which is carried out at a pressure slightly above atmospheric pressure; VSA (Vacuum Swing Adsorption = Vacuum Swing Adsorption) processes for which the adsorption phase is carried out at a pressure of the order of atmospheric pressure and regeneration under vacuum; VPSA processes and the like (MPSA, MSA ...) with an adsorption phase taking place under a few bars and regeneration under vacuum. This category also includes systems that are regenerated by flushing with a purge (or elution) gas, which gas may be external to the process itself. In this case, the partial pressure of the impurities is indeed lowered, which allows them to be desorbed.
    [0002] The adsorbent is used in reactors which will be called subsequently adsorbers. These adsorbers are also of different types according to their geometry. The simplest adsorber is cylindrical in shape with a vertical axis. When the flows to be purified become important, cylindrical adsorbers with horizontal axis can be used. Beyond a certain flow rate and / or if one seeks low pressure drops and / or if the speed of the gas may be greater than the speed of attrition (of movement of the balls) at least in certain stages of the cycle it becomes interesting to use a radial adsorber. For example, since the flow rates to be purified reach a few tens of thousands of actual cubic meters (that is to say, counted under the operating conditions) per hour, it is actually known to use radial adsorbers such that US Pat. No. 4,541,851 or US Pat. No. 1,638,669. The radial adsorbers make it possible to reliably perform the purification or the separation of large quantities of fluid by permitting, because of their geometry, great freedom of choice for the flow velocities of said fluids, in particular to make them compatible with the mechanical properties of the adsorbent particles used, while ensuring a good gas distribution through the adsorbent masses. This flexibility is due to the fact that the gas passage section is a function of the diameter and height of the grids and not just the diameter as for a standard adsorber. They are therefore particularly used for the drying and decarbonation of air before cryogenic fractionation, in the case of oxygen VSA and are particularly well adapted to VSA or PSA CO2, units having to process very high flow rates (several hundred thousand of Nm3 / h) in low (1 to 3 bar abs), average (less than or equal to 15 bar abs) or even relatively high (greater than 15 bar abs) pressure, with regeneration under vacuum, at atmospheric pressure or under pressure. The adsorption and regeneration pressures are chosen according to the overall process.
    [0003] There are many configurations for the use of radial adsorbers. Referring to FIG. 1 and taking the adsorption phase as a reference, the gas can flow from the inside to the outside (centrifugal circulation F) or from the outside to the inside (centripetal circulation P). The gas can enter from the bottom 3 or from the top 1 and exit the same from the bottom 2 or from the top 4. Depending on the case the gas will go from top to bottom (b) or from bottom to top (h) in the central part or the periphery. With reference to FIG. 1, it is therefore possible to have adsorptive centrifugal circulation of the type for example (successive directions: 1-bFb-2) with entry from the top and exit from below or else (successive directions: 1-bFh -4), the inlet and outlet being then in the upper part by separate pipes.The regeneration can be done in the same direction as the adsorption (regeneration co-current) or more generally in the opposite direction (regeneration against the current Other more complex configurations have been used Another possible arrangement is for example to add a circular sealing disk to split the adsorbent mass in two parts, it being possible in the same radial adsorber to have in phase adsorption, for example a centrifugal circulation in a first volume of adsorbent followed by a centripetal circulation in the upper volume of adsorbent, or for example for an entry at the bottom and u exit at the top [successive directions: 3-h-F-h-P-h-4]. It is known that the atmospheric air contains compounds to be removed before the introduction of said air in the heat exchangers of the cold box of an air separation unit, in particular the carbon dioxide (CO2) compounds, steam vapor water (H 2 O), nitrogen oxides and / or hydrocarbons, for example. Indeed, in the absence of such pretreatment of the air to remove its impurities CO2 and water, there is an ice solidification of these impurities during the cooling of the air at cryogenic temperature typically less than or equal to -150 ° C, which may result in clogging problems of the equipment, including heat exchangers, distillation columns ... In addition, it is also customary to at least partially eliminate the hydrocarbon impurities and nitrogen oxides may be present in the air to avoid their too high concentration in the bottom of the distillation column or columns, and thereby any risk of degradation of equipment. Conventionally, an air purification process cycle TSA comprises the following steps: a) purification of the air by adsorption of the impurities at superatmospheric pressure and at ambient temperature; b) depressurization of the adsorber to atmospheric pressure; c) regeneration of the adsorbent at atmospheric pressure, especially by the waste gases, typically impure nitrogen from an air separation unit and heated to a temperature usually between 100 and 280 ° C by means of one or more heat exchangers; d) cooling at ambient temperature of the adsorbent, in particular by continuing to introduce said waste gas from the air separation unit, but not reheated; e) repressurization of the adsorber with purified air from, for example, another adsorber in the production phase or optionally with the air to be purified.
    [0004] Generally, the air pretreatment devices comprise two adsorbers, operating alternately, that is to say that one of the adsorbers is in the production phase, while the other is in the regeneration phase. The production phase corresponds to the purification of the gaseous mixture by adsorption of the impurities. The regeneration phase comprises the depressurization, heating, cooling and repressurization steps mentioned above.
    [0005] A step of paralleling the two adsorbers, more or less long, that is to say, from a few seconds to several minutes, is usually added at the beginning or end of the regeneration phase. The operation of a radial adsorber for such an application is shown in FIG. 2. The fluid to be purified or separated 1 enters the lower part of the radial adsorber 10, passes through the adsorbent mass 20 and the purified fluid leaves the upper part 2. During regeneration, the regeneration fluid 3 enters the countercurrent by the upper part, desorbs the impurities contained in the adsorbent mass 20 and the waste gas 4 leaves at the bottom. The adsorber itself 10 consists of a cylindrical shell of vertical axis AA and 2 funds. The adsorbent mass is held in place by means of a perforated outer grid 11 and an internally perforated internal grid 12 fixed on one side to the upper bottom and on the other side to a solid plate 13 in the lower part. The fluid to be purified or separated 1 circulates vertically at the periphery in the external free zone 14 between the cylindrical shell and the external grid, passes radially through the adsorbent mass 20 and then flows vertically in the internal free zone 15 before leaving the adsorber by the top. Regeneration is carried out in the opposite direction.
    [0006] In practice, the adsorbent material may consist of one and the same adsorbent, for example zeolite X or doped activated alumina, or may comprise several beds. Among the multiple beds, mention may be made of activated alumina / zeolite X, silica gel / zeolite X, zeolite X / zeolite exchanged pairs). It may also be advantageous to use multilayers of the type: water-resistant silica gel, standard silica gel or activated alumina, zeolite X or of the type: silica gel or activated alumina, zeolite X, zeolite exchanged.
    [0007] FIG. 3 represents a radial adsorber comprising two distinct layers of adsorbents. This adsorber also includes other internal equipment (filter, distribution cone ...) which will be discussed later. In FIG. 3, three perforated grids 5, 6, 7, their lower base 8, the connecting pieces between the grids and a bottom 12, the two bottoms 10 and 11 and the outer shell 9 are observed. hold in place the adsorbents constituting the annular shaped beds 3 and 4. The connecting pieces 12 may be of different shapes and sizes depending on the exact technology adopted for the adsorbers. They may for example include removable hatches to access inter-grid spaces or the space between outer gate and ferrule. In other designs, these are only parts for fixing the grids with their ends. They are generally designed to avoid preferential gas paths in the upper part. They ensure of course a perfect seal between the internal and external gas volumes to avoid any bypass (input / output) that would render inoperative the purification process.
    [0008] Other elements, such as a filter in the central cylindrical space, a connection piece between the flange and said filter, a distribution cone internal to the filter, can complete the adsorber. The flow direction of the gas in the adsorption and regeneration phase (centrifugal or centripetal) is not left to chance but depends on process constraints or technological constraints. In a PSA where the flow decreases from the inlet to the outlet, the centripetal direction is generally chosen for the adsorption. The passage sections in this case decreasing, from the external grid to the internal grid, this makes it possible to maintain the speed of circulation of the gas and thereby limit the resistance to transfer of material in the fluid film surrounding the particles of adsorbent, which could otherwise become dominant and change the kinetics. In addition, the elution stage being in the opposite direction, it also allows to have the largest passage sections at the end where the outflow is the highest and to minimize the pressure drop during this crucial step in terms of performance. There are cases however where it is appropriate to adopt the centrifugal circulation solution. In the case of multi-beds, it often happens that the first layer of adsorbent acts as a guard bed with respect to an impurity present in low concentration in the feed gas and that the volume of this layer is small relative to the total volume of adsorbent. A typical order of magnitude is 5 to 10%. Located on the periphery of the adsorber, this layer could represent only a few centimeters on the width of the bed. Technologically, it becomes difficult to produce an adsorber with very closely spaced grids (threading problems, construction tolerances, in particular). In this case, it is often preferred to have this first layer on the inside, where the thickness, by simple geometry, can be for example 3 times greater for the same volume. The vast majority of TSA have centripetal adsorption for reasons of cost and / or energy consumption. It should first be noted that for the vast majority of TSA processes, the impurity or the impurities to be arrested are either in the form of traces or in any case very minor in the feed gas. This is the case cited above for air purification, but also gas drying and purifications such as syngas before cryogenic hydrogen / carbon monoxide separation, natural gas, stopping volatile organic compounds, etc. The flow of feed gas between the inlet and the outlet varies little and is not a criterion for the choice of direction of circulation. Once saturated, the adsorbent is regenerated by circulating a gas at a high temperature, generally between 100 and 280 ° C. For the sake of optimization, during the heating phase, it is common to introduce only the amount of heat required, which means that at the outlet the gas never leaves with a very high temperature. For a regeneration temperature of 150 ° C, the peak temperature, that is to say the maximum output temperature may be 50 to 60 ° C for example. In order to avoid having to heat the outer shell with the regeneration gas, which would imply both an energy loss and the need to invest in an insulation, it is common to bring the regeneration gas into the part. central of the radial adsorber. There is thus no heat loss to the external environment and the outer shell which sees only a moderate temperature, does not need to have a thermal insulation. Regeneration is therefore conventionally carried out centrifugally and the adsorption which is in the opposite direction is therefore centripetal: the atmospheric air is introduced through a bottom, circulates at the periphery between ferrule and outer gate, passes radially through the adsorbent mass, is collected, dry and decarbonated, in the center and evacuated by one of the funds. Radial adsorbers are generally made of carbon steel for reasons of cost, although it is known that carbon steel is moderately resistant to corrosion despite the protective layer that it naturally develops on its surface and that the atmospheric air exhibits a tendency to corrode especially because of its moisture and the presence of carbon dioxide. However, the corrosion associated with the usual impurities of the atmospheric air and the operating conditions of these adsorbers is sufficiently low that a corrosion allowance of a few millimeters (usually 2 to 3) is sufficient to ensure that the minimum thickness required for mechanical strength for periods well in excess of 10 years. There are, however, industrial sites where the air is more polluted than normal or locations, such as on the seafront for example or on barges at sea, on gas or oil fields, for which a mere extra thickness of corrosion could be quickly inadequate. Some constituents are likely not only to rapidly corrode carbon steel but also to chemically attack certain adsorbents and destroy them. One solution is to put upstream of the TSA process of air purification, called FEP, a pretreatment. In a chemical plant where the air could periodically contain for example traces of HCI, it can be installed a "filter" at low pressure, the suction of the air compressor for example. This equipment will for example be an adsorber, also of radial type, containing a lost charge of a constituent stopping traces of HCl. A bed of 13X zeolite or activated alumina usually works. More specific products may however be used if necessary. The charge is renewed periodically, every 6 months for example.
    [0009] In a certain number of cases, a simple filter is not sufficient because the corrosive species may be of several types and / or too large a quantity for this type of solution. Without going into details here, it is known that many constituents such as chlorine, fluorine, SO42-, NO3- or caustic compounds can locally destroy the natural protection developed by carbon steel and attack the metal in depth. . Oxygen and water in the air are an aggravating factor. The operating conditions of the equipment (temperature, presence of liquid water during regeneration, etc.) also play an accelerating role of corrosion. These adverse conditions are found in some sites, particularly where some ores (copper in particular) are processed. The air is then washed through columns, often packed to limit the pressure drop.
    [0010] Additives are added to the water depending on the nature of the impurities to be removed. The last washing is usually carried out with water to avoid any entrainment of chemicals to the downstream equipment, in particular FEP. This is then the subject of a standard design. If this solution has proven its effectiveness, it remains nonetheless that it has at least three drawbacks: its cost (large diameter columns, cost of additives), energy consumption (pumping means washing, pressure drop on low pressure air) and the pollution of a large quantity of water (with very diluted impurities or chemicals formed). Increasingly stringent anti-pollution standards make it necessary to treat these washing waters before any discharge, which requires large-scale installations that are costly in terms of investment (pond, storage) and operation (chemicals, pumping, analyzes).
    [0011] Starting from there, a problem is to find a new way to deal with these problems of impurities. A solution of the present invention is a purification plant by adsorption of a gaseous flow comprising at least one corrosive impurity vis-à-vis carbon steel, comprising a radial adsorber comprising: - a ferrule with an outer steel casing carbon; - a vertical perforated internal grid of corrosion resistant material; - an external grid vertical and perforated; an adsorbent maintained vertically by the external grid and the internal grid making it possible to at least partially stop said corrosive impurity; and means for centrifugal circulation of the gas stream. The term "corrosion-resistant material" means a non-corrodible material, ie physically or chemically insensitive to the compounds in contact, or having a sufficiently low corrosion rate for a standard corrosion allowance, generally from 1 to 5 mm, allows a lifetime of equipment greater than 10 years, more generally compatible with the expected life of the unit. In the context of the present invention, this means in particular that it is not ordinary carbon steel, without particular surface treatment; "Perforated grid": a gas-permeable system impermeable to adsorbent particles and having sufficient mechanical characteristics to ensure that the purification plant operates for several years; in other words, the grid will hold in time and keep the adsorbents in place; - "internal grid": the grid closest to the central axis; and "external grid": the grid closest to the outer wall of the adsorber.
    [0012] A perforated grid may be composed of several elements, for example a grid of thickness 6 or 8 mm with large openings on which is plated a metal fabric opening less than mm. In general, for a radial adsorber, depending on the number of different adsorbents used, intermediate grids are added. In practice, if N is the number of adsorbent layers, N-1 intermediate grids must be used, ie at all N + 1 grids. As an example of means of centrifugal circulation of the gas flow include the inlet pipe in the adsorber, the central void volume, the possible central gas distribution system, the interpart between the ferrule and the outer gate, the tubing outlet in a bottom, the deflector and any filters, which can be associated valves and different pipes.
    [0013] Depending on the case, the installation according to the invention may have one or more of the following characteristics: said installation is of the TSA type and comprises means for circulating the regeneration gas in a centripetal manner. Thus, the regeneration gas loaded with the impurities will leave it through the center of the adsorber which is provided for such aggressive conditions (acidic conditions); the equipment of the installation in contact with the regeneration gas at the outlet of the adsorber is made of a material resistant to corrosion; said installation is of the PSA type and comprises means for circulating the waste gas in a centripetal manner; - the equipment in the installation in contact with the waste gas is made of a material that is resistant to corrosion. Without wishing to go into the details of the PSA cycles widely described in the literature, the waste gas is extracted countercurrently from the feed gas during steps commonly known as "final decompression against the current" (or Blow Down) and "elution" (or purge). This waste gas is extracted at a lower pressure than the adsorption pressure and contains the most strongly adsorbable constituents. It will be noted that this waste gas may constitute the fraction that is to be produced. It will be called here nevertheless residual gas in all cases; - The corrosion resistant material is selected from stainless steels, noble metals, polymers, ceramics and carbon steel coated with an anticorrosive material. By anticorrosion material is meant painting, galvanizing, electro-zincage, stainless steel plating, teflon deposit, in particular.- the outer gate is carbon steel. Note that in the case where several adsorbents would be used, the intermediate grids are made of carbon steel; - At least one bottom of the adsorber is carbon steel, preferably the two funds of the adsorber are carbon steel. This assumes that they are not in contact with the corrosive impurities. This is generally possible as shown in Figure 3 where the funds 10 and 11 do not see the gas to be treated, or the regeneration gas output. This applies to ASDs (subject of the description) but also to PSAs or guard beds; the adsorbent maintained vertically rests on a support having a slope directed towards the central axis of the adsorber. The lower support of the adsorbent layer is generally flat for even distribution of gas flows through the adsorbent. Nevertheless, this support is sometimes curved for a better mechanical resistance. This is the case for example in Figures 2 and 3.
    [0014] For an installation according to the invention, the inner part of this lower support has a slope directed towards the center (unlike the support of FIGS. 2 and 3) in order to facilitate the gravitational flow of the liquids possibly formed during the cycle. towards the internal part of the adsorber, then from there, towards the low point of the installation from where they will be preferentially evacuated via a purge. It may be a curved bottom, but installed in the "opposite" direction to that shown in Figures 2 and 3; said installation comprises at least one means for collecting and extracting liquids from the adsorber originating from the gas stream to be purified and / or formed during the regeneration. These liquids can be extracted from the installation by a valve opening on a purge circuit with said valve preferably automated and linked to the adsorption cycle; the adsorbent maintained vertically is chosen from silica gel, porous glass, resins, silicalite, activated carbon and zeolite 3A; Some adsorbents may also be chemically attacked by corrosive impurities for carbon steel. To avoid having to change the adsorbents or at least that of the first layer too quickly, it is necessary to retain adsorbents also resistant to these impurities, even if they are less effective as adsorbents. Among them, mention may be made of the adsorbents just mentioned, that is to say microporous glass, zeolite 3A (which will selectively adsorb water), certain silica gels, silicalites. Activated charcoal also has good acid resistance. Other particularly resistant adsorbents are insoluble macromolecules of the polymer type, for example based on crosslinked polystyrene or polyacrylate, comprising macro and / or microporosities of size enabling them to adsorb and / or condense the moisture of the gas. treat. Among them, the various ion exchange resins can be a relatively inexpensive adsorbent to perform at least a first part of the drying. Note that in addition to the internal grid which holds the adsorbent mass in place, the central portion may comprise, as previously described, a filter and / or a gas distributor, for example a perforated tube or a cone, as well as connecting pieces. between the inlet / outlet flange and these elements. These elements are preferably in corrosion resistant material. Note however that some of these equipment can be changed relatively easily and it is possible to consider them as parts to be replaced periodically that will be made of carbon steel. This is an economic choice to make according to various parameters (material costs, lifetime, maintenance policy). The subject of the invention is also a process for purifying a gaseous flow comprising at least one corrosive impurity with respect to carbon steel, implementing an installation according to the invention and in which the corrosive impurity is selected: - in the group of acids: HCl, HNO3, HF, and H2SO4; or - in the group of gases: NOx, SOx and H2S in the presence of moisture. Preferably the gas stream is a gas stream from combustion, preferably oxycombustion, or from the metallurgy, preferably blast furnace gas. It should be noted that the process according to the invention may be a CO2 drying or deballasting process. According to one particular case, the invention relates to a process for purifying a gaseous flow comprising at least one corrosive impurity with respect to carbon steel, implementing an installation according to the invention comprising at least one means of collecting and extracting liquids from the adsorber from the gas stream to be purified and / or formed during regeneration and wherein the corrosive impurity is selected: - in the group of acids: HCl, HNO3, HF, and H2SO4; or - in the group of gases: NOx, SOx and H2S in the presence of moisture; and the liquids extracted from the adsorber are recycled in acidic water or acid production processes.
    [0015] The invention will now be described in detail in the context of a CO2 capture process. It is recalled that in order to reduce the CO2 emissions of human origin in the atmosphere, it is necessary to extract CO2 from a gas generated by an industrial process, possibly to purify it and finally, in general, to compress it to transport it in a pipeline. This treatment generally requires at least partially drying the CO2.
    [0016] Gases from Oxycombustion processes are good candidates because they have a high CO2 content, the nitrogen being removed from the air before combustion. These gases also contain a percentage of NOx (NO & NO2 mainly) resulting from combustion. These NOx will enter the adsorbers to dry CO2 in the form of NO, NO2 and also in the form of nitric acid (HNO3) resulting from the conversion of NO to NO2 and NO2 to HNO3, especially if the purification takes place after compression and cooling. HNO3 is retained by adsorbent adsorbers and NO and NO2 are partially retained. In the adsorber, the reactions of NO to NO2 and NO2 to HNO3 are accelerated and the equilibria are shifted to HNO3 formation. At the time of regeneration of the adsorbent, during the desorption of previously adsorbed NOx, it is also possible to form nitric acid in the presence of water trapped during adsorption. The hot nitric acid formed and / or desorbed during regeneration as well as the desorbed water vapor will tend to condense on the colder zones located towards the outlet of the adsorber. The condensates formed will then contain a high concentration of nitric acid. Referring now to Figure 4 which shows a radial adsorber 10 according to the invention.
    [0017] The dimensions of this adsorber will depend on the gas flow to be dried and the operating conditions. In general, the diameter of the ferrule varies from 2 meters to 6 meters and its height from 4 to more than 20 meters. The oxycombustion gas 1 to be dried is introduced at the top, is distributed by means of the distributor 16 through the adsorbent mass 30, which is here a single bed of silica gel. This bed is held in place by the grids 14 and 15 to which the bottom 21 is fixed. The dried gas 2 circulates in the interpart 17 and then leaves through the lower part of the adsorber. The regeneration gas 3 is introduced countercurrent first hot (heating step) and then at room temperature (cooling step). It exits the adsorber through the center and the upper bottom 4. The regeneration taking place at 200 ° C, insulation by simple gas blade 21 was provided. The gas contained in this blade is in equipressure with the gas circulating in the interparoi.
    [0018] The connection between the two gas volumes is here provided in the upper part to limit convection phenomena but other locations are possible depending on the criterion. The liquids formed are collected by gravity in the volume 18 situated at the bottom point of the support base 21. These liquids can come from droplets present in the gas to be treated 1, the distributor 16 acting as a gas / liquid separator or as already described in FIG. condensation of steam during the regeneration phase on the colder parts downstream. The shape of the bottom support 21 promotes the entrainment of liquids to the central portion and the volume 18. These liquids are purged via the pipe 19 and the valve 20. The volume 18 and the pipe 19 will be advantageously isolated to avoid revaporization Liquids 5. These highly concentrated liquids will be advantageously treated prior to their release or used possibly for other applications. Among the latter, we can mention the more efficient gas washes with acidic water, or for example the washing of coal or coal residues after combustion to extract the metals (iron, arsenic, mercury, vanadium ... ) in order to valorize these constituents or to remove them preventively from the coal. These condensates can also be used as raw material for acid production.
    [0019] The internal elements of the adsorber 10, such as the grids 14 and 15 and the pipe 19 for example, are designed so that their differential thermal expansion between the stages of the TSA cycle (adsorption and regeneration) or between the different elements at a given moment of the cycle do not lead to irreversible deformations jeopardizing the proper functioning of the installation of the invention (loss of gas tightness, thickness of the adsorbent mass significantly heterogeneous ...). For example, the pipe 19 may have the shape of a turn (not shown in Figure 4). The upper flange, the distributor 16, the internal grid 15, the junction piece between the flange and the internal grid, the reservoir 18, the bottom support 21, the pipe 19 and possibly the valve body 20 are made of stainless steel of the type NAG (Nitric Acid Grade) is a quality of steel that is resistant to nitric acid. The shell 11 and the bottoms 12 and 13, the external grid 14, the envelope of the insulating blade are made of carbon steel.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. An adsorption purification plant for a gaseous flow comprising at least one corrosive impurity with respect to carbon steel, comprising a radial adsorber comprising: a ferrule with an outer casing of carbon steel; - a vertical perforated internal grid of corrosion resistant material; - an external grid vertical and perforated; an adsorbent maintained vertically by the external grid and the internal grid making it possible to at least partially stop said corrosive impurity; and means for centrifugal circulation of the gas stream.
    [0002]
    2. Installation according to claim 1, characterized in that said installation is TSA type and comprises means for circulating the regeneration gas centripetally.
    [0003]
    3. Installation according to claim 2, characterized in that the equipment of the installation in contact with the regeneration gas at the outlet of adsorber are of corrosion resistant material.
    [0004]
    4. Installation according to claim 1, characterized in that said installation is PSA type and comprises means for circulating the waste gas centripetally.
    [0005]
    5. Installation according to claim 4, characterized in that the equipment of the installation in contact with the waste gas are corrosion-resistant material.
    [0006]
    6. Installation according to one of claims 1 to 5, characterized in that the corrosion resistant material is selected from stainless steels, noble metals, polymers, ceramics and carbon steel coated with an anticorrosive material .
    [0007]
    7. Installation according to one of claims 1 to 6, characterized in that the outer gate is carbon steel.
    [0008]
    8. Installation according to one of claims 1 to 7, characterized in that at least one bottom of the adsorber is carbon steel; preferably the two funds of the adsorber are carbon steel.
    [0009]
    9. Installation according to one of claims 1 to 8, characterized in that the adsorbent held vertically based on a support having a slope directed towards the central axis of the adsorber.
    [0010]
    10. Installation according to one of claims 1 to 9, characterized in that said installation comprises at least one means for collecting and extracting liquids from the adsorber from the gas stream to be purified and / or formed during regeneration.
    [0011]
    11. Installation according to one of claims 1 to 10, characterized in that the adsorbent maintained vertically is selected from silica gel, porous glass, resins, silicalite, activated carbon and zeolite 3A.
    [0012]
    12. Process for purifying a gaseous flow comprising at least one corrosive impurity with respect to carbon steel, implementing an installation as defined in one of Claims 1 to 11 and in which the impurity corrosive is selected: - in the group of acids: HCl, HNO3, HF, and H2SO4; or - in the group of gases: NOx, SOx and H2S in the presence of moisture.
    [0013]
    13. The method of claim 12, characterized in that the gas stream is a gas stream from combustion, preferably oxy-combustion, or from the metallurgy, preferably blast furnace gas.
    [0014]
    14. Method according to one of claims 12 or 13, characterized in that said process is a CO2 drying or deballasting process.
    [0015]
    15. A method for purifying a gaseous flow comprising at least one corrosive impurity vis-à-vis the carbon steel, implementing an installation as defined in claim 10 and wherein the corrosive impurity is chosen: in the group of acids: HCl, HNO3, HF, and H2SO4; or - in the group of gases: NOx, SOx and H2S in the presence of moisture; and the liquids extracted from the adsorber are recycled in acidic water or acid production processes.
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    同族专利:
    公开号 | 公开日
    US20170173515A1|2017-06-22|
    PL3122439T3|2020-10-19|
    EP3122439B1|2020-07-08|
    WO2015145001A1|2015-10-01|
    EP3122439A1|2017-02-01|
    CN106385797A|2017-02-08|
    FR3019060B1|2017-12-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3162516A|1961-08-14|1964-12-22|Richard E Dwyer|Method of filtering exhaust gases|
    DE3342447A1|1982-11-25|1984-05-30|Linde Ag, 6200 Wiesbaden|Adsorber unit and process for operating the same|
    GB2189409A|1986-04-18|1987-10-28|Cannon Ind Ltd|Protective coatings for metals|
    US20030205130A1|2002-05-01|2003-11-06|Neu Bernard Thomas|Radial adsorption gas separation apparatus and method of use|
    WO2010001038A2|2008-07-03|2010-01-07|L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|Dust-laden wet gas treatment|
    FR2937257A1|2008-10-21|2010-04-23|Air Liquide|CONSTRUCTION METHOD APPLICABLE TO LARGE SIZE RADIAL ADSORBERS|
    FR2962663A1|2010-07-16|2012-01-20|Air Liquide|ADSORBER WITH INTERNAL COATING|
    US20120079938A1|2010-10-05|2012-04-05|Celik Cem E|Radial bed vessels having uniform flow distribution|
    FR2541588B1|1983-02-28|1985-07-05|Air Liquide|CONTAINER AND PURIFICATION PLANT BY ADSORPTION|
    FR2856607B1|2003-06-27|2006-08-18|Air Liquide|ACCELERATED TSA CYCLE AIR PURIFICATION METHOD|
    CN102580626B|2012-03-20|2013-10-02|南京国昌化工科技有限公司|Double-shaft radial flow reactor|CN107213770A|2017-07-03|2017-09-29|江苏新世纪江南环保股份有限公司|Desulfuration absorbing tower and its method for building up and operation method|
    CN107899388B|2017-11-23|2020-08-18|浙江海洋大学|Fluorine-containing waste gas treatment process|
    CN108043188B|2017-11-23|2020-08-18|浙江海洋大学|Organic waste gas purification process for adhesive products|
    CN113069878A|2021-04-28|2021-07-06|山东大学|Lateral flow VOCs adsorption regeneration unit, device and system|
    法律状态:
    2016-03-21| PLFP| Fee payment|Year of fee payment: 3 |
    2017-03-22| PLFP| Fee payment|Year of fee payment: 4 |
    2018-03-23| PLFP| Fee payment|Year of fee payment: 5 |
    2020-03-19| PLFP| Fee payment|Year of fee payment: 7 |
    2021-03-23| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452705A|FR3019060B1|2014-03-28|2014-03-28|INSTALLATION AND METHOD FOR ADSORPTION PURIFICATION OF A GAS FLOW COMPRISING A CORROSIVE IMPURITY|FR1452705A| FR3019060B1|2014-03-28|2014-03-28|INSTALLATION AND METHOD FOR ADSORPTION PURIFICATION OF A GAS FLOW COMPRISING A CORROSIVE IMPURITY|
    PL15709721T| PL3122439T3|2014-03-28|2015-02-19|Facility and method for purification by adsorption of a gaseous flow comprising a corrosive impurity|
    CN201580026549.0A| CN106385797A|2014-03-28|2015-02-19|Facility and method for purification by adsorption of a gaseous flow comprising a corrosive impurity|
    EP15709721.3A| EP3122439B1|2014-03-28|2015-02-19|Facility and method for purification by adsorption of a gaseous flow comprising a corrosive impurity|
    PCT/FR2015/050403| WO2015145001A1|2014-03-28|2015-02-19|Facility and method for purification by adsorption of a gaseous flow comprising a corrosive impurity|
    US15/129,638| US20170173515A1|2014-03-28|2015-02-19|Facility and method for purification by adsorption of a gaseous flow comprising a corrosive impurity|
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